Basic derivatives of fatty acids and a process for their manufacture



Patented Mar. 7, 1939 BASIC DERIVATIVES OF FATTY ACIDS AND A PROCESS FOR THEIR MANUFACTURE Valentin KartaschofLBasel, Switzerland, assignor to Chemical Works formerly Sandoz, Basel, Switzerland No Drawing. Application October 19, 1937, Se-

{$316 No. 169,918. In Switzerland October 23,

ll-Claims.

The present invention relates to new basic derivatives of fattyacids and to a process for their manufacture, which products are valuable compounds possessing wetting, emulsifying and deterging properties and which are able to form with substantive dyestuffs water insoluble or diflicultly soluble lakes.

I have found that by interaction of hydroxylated polyamines with fatty acids containing at least 8 carbon atoms or with their esters new valuable compounds may be obtained, which are generally carboxylic acid esters of the polyamines The hydroxylated polyamines used according to the present invention are prepared by condensation of a- -glycerinedichlorhydrine or of glycerineepichlorhydrine with hydroxalkylamines like mono-. diand triethanolamine, propanolaminesand the like. If a-y-glycerinedichlorhydrine is condensed withthe ethanolamines, several compounds which may be called polypropanolpolyethanolamines can be obtained, this according to the amine used. If monoethanolamine is used and the condensation is carried out at an elevated temperature, high molecular hydroxylated polyamines of the formula:

CzH4OH on CH4OH OH- 110 1111 011 will be obtained. If diethanolamine is used, the obtained polyamines possess beside at least one tertiary amino group also one or more quaternary ammonium groups and respond therefore to the following probable formula:

zH4 h 0H 2114 1): 11 (C:H4OH) If finally a tertiary hydroxylated base like triethanolamine, or diethylethanolamine is used, quaternary polyamines will be obtained possessing for example the following formula These hydroxylated polyamines are obtained by heating hydroxylated amines together with a-v-glycerinedichlorhydrine or epichlorhydrine, eventually in presence of water and of acid binding agents at a temperature which may vary between 60" and 200 C. according to the art of the amine used. It has generally been observed that higher temperatures arenecessary to produce quaternary compounds, whereas the preparation of secondary and tertiary amines may in presence of small quantities of an alkali and in'absence of water, with fatty acids containing at least 8 carbon atoms or with their esters at a. temperature of about 100-250 C. At this temperature the fatty acids or their esters condense with the hydroxylated polyamines, whereby carboxylic acid esters and eventually amides are I produced.

As fatty acids are preferably used lauric, oleic, palmitic, stearic, naphthenic acids or their mixtures as obtained by the saponification of fats and oils. Suitable fatty acid esters are for instance the coconut fat, woolfat, castor oil, oleine, hardened fats, tallow and also waxes such as spermaceti and'the like.

In order to carry out the condensation of the hydroxylated polyamines with the fatty acids or their esters, the polyamir as must be used as free bases, and the heating preferably carried out in presence ofalkali, suchas sodium, potassium and calcium hydroxide which act as catalysts for the splitting off of water. During the condensation it is further advantageous to eliminate the water produced during the reaction by distilling it on from the recipient in which the reaction is carried out. After the condensation has occurred, which point is generally reached after some hours of heating, the reaction products obtained are allowed to cool down and are preferably transformed into their water soluble salts, by treating them preferably when they are still warm, with aqueous solutions of organic or inorganic acids. The salts thereby obtained can then be used for various purposes.

The compounds obtained according to the present invention are more or less colored products of oily or waxy consistence, easily soluble in dilute organic and inorganic acids, yielding clear or opalescent solutions. They possess a soapy character and give foaming solutions, which are generally stable towards hard water andare useful for deterging and. washing various textile materials.

According to the fatty acid used for the preparation of the new compounds they possess also process possess the property to form with substantive dyestuffs water insoluble or difiicultly soluble addition products, and can therefore advantageously be used for increasing the fastness properties of dyeings with dyestuffs of this class.

One object of the present invention is the process for the manufacture of new basic derivatives of fatty acids containing at least 8 carbon atoms, consisting in heating hydroxylated polyamines with fatty ."cids or their esters at a temperature of 100-250 C., preferably in presence of an alkali and eventually transforming the condensation products thus obtained into their water soluble salts.

Another object of the present invention are the new basic derivatives of fatty acids and their water soluble salts prepared as described above.

Still another object of the present invention is the use of the new basic derivatives of fatty acids for various purposes in the textile, dyeing and allied industries.

The following examples, without being limitative, illustrate the present process, the parts being by weight:

. Example 1 61 parts of monoethanolamine are heated under stirring to 110 C. and 65 parts of a-y-glycerinedichlorhydrine are slowly added thereto in such a manner that the temperature of the reaction remains between 128 and 130 C. After one and half an hour the condensation is realized and the reaction mass allowed to cool down to about 100 C. At this temperature 40 parts of sodium hydroxide are added thereto and the mixture stirred until it becomes completely solubilized. The reaction mass is then heated up to 130 C., whereby water-amine mixture distills off. After A; hour 60 parts of molten coconut fat are added and the mixture is heated under good stirring. At 194 C. the reaction takes place under foaming and at 211 C. the whole mass becomes completely homogeneous. After cooling down to about 100 C., the obtained basic product is diluted with about 100 parts of water and acidulated with acetic acid to a pH of about 6. A yellowbrownish paste possessing a soap-like character is obtained.

Example 2 k To the hydroxylated polyamine obtained according to Example 1 are added at 178 C., after treatment with sodium hydroxide, 60 parts of castor oil and heated during one hour at 215 C. After this time a sample taken out and acidulated with acetic acid is soluble in water giving a slightly opalescent solution. The reaction product is then allowed to cool down and is transformed in its water-soluble salt by treatment with acetic or lactic acid.

A pale yellowish paste possessing wetting and deterging properties is obtained.

Example 4 93 parts of diethanolamine are heated up to 110-115 C. and treated with 65 parts of a- -glycerinedichlorhydrine in such a manner, that the reaction temperature remains at 130-135 C. The obtained condensation product is then allowed to cool down to about 100 C. and 40 parts of sodium hydroxide are added thereto. The whole mass is then stirred until it becomes homogeneous, then heated up to 170 C. At this temperature 60 parts of melted 'coconut fat are added thereto and the temperature raised up to 202-20'7 C. The reaction mass becomes very rapidly homogene and soluble in acid solutions. The condensation product thus obtained is then allowed to cool down and acidulated with acetic acid at a pH of about 6. It is a yellowish paste soluble in water, possessing wetting-out properties and useful as levelling agent in the dyeing with basic dyestuffs.

Example 5 To the hydroxylated polyamine obtained as described in Example 1 are added, after treatment with alkali, 50 parts of hardened fat and heated up to 208 C. At this temperature the condensation takes place very rapidly with production of foam and a yellowish paste soluble in acids is obtained. This condensation product can advantageously be used as softening agent for textiles and for increasing the fastness properties of dyeings made with substantive dyestuffs. When acidulated with acids to a. pH 6, it .can be used instead of soap for the development of vat discharges on substantive grounds.

Example 6 The hydroxylated polyamine prepared according to Example 1 is condensed in presence of a small quantity of alkali at 203 with 50 parts of tallow until a sample shows that the reaction product is clearly soluble in acid solutions. The brownish paste thus obtained possesses softening properties.

Example 7 The hydroxylated polyamine prepared according to Example 4 is heated in presence of a small quantity of potassium hydroxide with parts of melted spermaceti during about 3 hours at 215-230 C. A yellowish-brown wax-like product, soluble in acids to an opalescent solution and possessing softening properties for textiles, is obtained.

Example 9 61 parts of monoethanolamine are heated up to 110 C. and treated with 65 parts of a v-glycerinedichlorhydrine in-such a manner, that the reaction temperature remains at about 130 C., after the reaction is terminated, diluted with 50 parts of water, 40 partsof sodium hydroxyde are added thereto. The reaction product is then stirred at 100C. untilthe alkali is dissolved,

heated under distilling ofi of water to 125 C., and treated at this temperature with 65 parts of aw-glycerinedichlorhydrine. After stirring for about 1 hours at 130-135 C. it is cooled down again to about 100 C., diluted with 70 parts of water and treated with 38 parts of sodium hydroxide at 100-107 C. When the mass becomes homogeneous, it is heated slowly up to 135 C. under distilling off of water. When the water is eliminated, the temperature raises to 150 C. and 60 parts of hardened fat are added thereto. The heterogeneous mixture thus obtained is then slowly heated up to 195 C. at which temperature the condensation takes place under foaming and is rapidly terminated. After cooling down and treatment with hydrochloric acid a clear yellowish paste, soluble in water, is obtained.

Example 10 93 parts of diethanolamine are condensed with 55 parts of epichlorhydrine in the manner described in Example 4 and after treatment with alkali hea'ted up to 150 C. At this temperature 50 parts of stearic acid are added thereto and the mass heated up to 205212 CL, whereby the condensation takes place very rapidly. The yellowish condensation product thus obtained is soluble in water to an opalescent, and in dilute acids to a clear solution possessing foaming properties. It can be used for softening textiles.

Example 11 61 parts of monoethanolamine are heated to 110 C. and treated with 65 parts of a-y-glycerinedichlorhydrine in such a manner, that the reaction temperature stands at 155-160 C. After the condensation the reaction mass is allowed to cool down, diluted with 50 parts of water, treated with 40 parts of sodium hydroxide and heated again to 135 C., in order to eliminate the water present therein. After the major part of water has been distilled off, '70 parts of naphthenic acids mixture of acid number 270 are added thereto and the temperature raised up to 210-215 C. The heating is carried out during 2 /2 hours, whereby the condensation occurs.

The brownish product thus obtained is soluble in dilute acetic acid yielding opalescent solutions, possessing goodwetting-out properties.

Example 12 acids to a clear solution possessing wetting-out and foaming properties.

What I claim is: I 1. A process for the manufacture of new basic derivatives of fatty acids, comprising the steps of condensing a hydroxyalkylamine with a body selected from the group consisting of n y-glycerinedichlorhydrine and epichlorhydrine; heating the hydroxylated polyamines thus obtained with a body selected from the group consisting of fatty acids containing at least 8 carbon atoms and of their esters, to a temperature of 100-250 C. and transforming the basic compounds thus obtained into their acid addition salts.

2. A process for the manufacture of new basic derivatives of fatty acids, comprising the steps of condensing a hydroxyalkylamine with a body selected from the group consisting of -glycerinedichlorhydrine and epichlorhydrine, heating the hydroxylated polyamines thus obtained with a body selected from the group consisting of fatty acids containing at least 8 carbon atoms and of their esters, to a temperature of 100-250 C. in presence of an alkali, and transforming the basic compounds thus obtained into their acid addition salts.

3. A process for the manufacture of new basic derivatives of fatty acids, comprising the steps of condensing a hydroxyalkylamine with a body selected from the group consisting of a y-glycerinedichlorhydrine and epichlorhydrine, heating the hydroxylated polyamines thus obtained with a body selected from the group consisting of fatty acids containing at least 8 carbon atoms and of their esters, to a temperature of 100-125 C. in presence of sodium hydroxide and in absence of large amounts of water, and transforming the basic compounds thus obtained into their acid addition salts.

4. A process for the manufacture of new basic derivatives of fatty acids, comprising the steps of condensing an ethanolamine with a body selected from the group consisting of ur -glycerinedichlorhydrine and epichlorhydrine, heating the hydroxylated polyamines thus obtained with a. body selected from the group consisting of fatty acids containing at least 8 carbon atoms and of their esters, to a temperature of 100- 125 C. in presence of sodium hydroxide and in absence of large amounts of water, and "transforming the basic compounds thus obtained into their acid addition salts.

5. A process for the manufacture of a new basic derivative of a fatty acid, comprising the steps of heating the hydroxylated polyamine obtained by interaction of mono-ethanolamine with a glycerinedichlorhydrine, at a. temperature of 194-211 C, in presence of sodium hydroxide with coconut fat and transforming the basic compound thus obtained by treatment with an acid into its water-soluble acid addition salt.

6. A process for the manufacture of a new basic derivative of a fatty acid, comprising the steps of heating the hydroxylated polyamine obtained by interaction of monoethanolamine with -glycerinedichlorhydrine, at a temperature of 194-211 C. in presence of sodium hydroxide with hardened fat at a temperature of about 208 C. and transforming the basic compound thus obtained by treatment with an acid into its watersoluble acid addition salt.

7. The process for the manufacture of a new basic derivative of a fatty acid, comprising the steps of heating the hydroxylated polyamine obtained by interaction of diethanolamine with a- -glycerinedichlorhydrine at a temperature of 202-207 C. in presence of sodium hydroxide with coconut fat and transforming the basic compound thus obtained by treatment with an acid into its water-soluble acid addition salt.

8. The basic derivatives of fatty acids with at least 8 carbon atoms, comprising fatty acid esters of hydroxylated polyamines, which are in form of their acid addition salts easily soluble in water, yielding soap-like solutions, which form with substantive dyestufl's water-insoluble or dif- 

